Cation-active polychloride containing an imidazoline ring and method of making same



Patented Nov. 13, 1951 UNITED STATES PATENT OFFICE CATION-ACTIVE POLYCHLORIDE CONTAIN- ING AN IMIDAZOLINE RING AND METHOD OF MAKING SAME Melvin De Groote, University City, and Bernhard Keiser, Webster Groves, Mm, assignors to Petrolite Corporation, Ltd., Wilmington, Del., a corporation of Delaware No Drawing. Original application March 11, 1948, Serial No. 14,395. Divided and this application February 18, 1949, Serial No. 77,291

10 Claims. (01. 260-3095) 1 2 This invention relates to new chemical prodis l-hydroxyethyl 2 heptadecenyl glyoxalidine, ucts or compounds and to the manufacture of the formula of which is as follows:

same, our present application being a division of N our co-pending application Serial No. 14,395 H H 1 filed March 11, 1948, now Patent 2,468,180, 5 2 ranted April 26, 1949. Nonzomon n object f ur inv ntion i t prov d a The reaction involving two moles of such new chemical compound or product that is parglyoxalidine and one mole of diglycol chloroticularly adapted for use as a demulsifier for formate proceeds in the following manner:

N-CH2 2 H CIIOCOCzHlOCzHAOCOICI C11H:3C\ Hi NCHzCHzOH ru r -r CnHuC CH2 CH2 CCnHaa ZHC] NCHzCH2O[OCOCzH4OC2H4OCO1OCHzCHz N-CH2 CHz-N II I ll (311E330 CH2 CH2 C CnHas l- Nomomowoooznloozmocoufonzonm H X H crude oil emulsions, but which is also capable A consideration of the reaction, or reactions of various other uses. which take place between these two classes of Another object of our invention is to provide a reagents, indicates that a varied and more compracticable method for manufacturing said new plex class of materials is obtainable than the chemical product or compounds. rather simple example noted in the formula im- The material, compound, product, or composimediately preceding. However, it may be well to tion of matter herein described consists of a catinclude specific examples before considering the ion-active p yc e Containing an da O- more elaborate derivatives. For convenience, the line ring. Such cation-active polychloride is obimidazolines, or oxyalkylated imidazolines, as the tained by reaction between: case may be, are referred to as an amine re (A) An oxyalkylated imidazoline substituted actant. in the 2-position by a radical containing from Diglycol chloroformate is a colorless, relatively 11-22 carbon atoms selected from the group connon-volatile organic liquid. It has a comparasisting of alicyclic hydrocarbon radicals, aliphatic tively high boiling point, and thus, lends itself hydrocarbon radicals substituted by hydroxyl to reaction by merely combining the chlororadicals; said oxyalkylated imidazolines containformate with a suitable oxyalkylated imidazoline ing a member of the class consisting of under a reflux condenser equipped with a suitable stirrer.

and Oxyalkylated imidazolines have been described in the literature, as, for example, in our U. S.

Patent N0. 2,369,818, dated February 20, 1945. What is said hereinafter is substantially as it apatoms, and n is the numeral 1 to 10; and pears in verbatim form in the aforementioned (B) Diglycol chloroformate, sometimes patent, with certaln obvious r eductlonin scope. ferred to as diethylene glycol bis (chloroformate), Thus, e speclfic m z hnes herein contemt formula f r such compound being as follow plated as reactants, are oxyalkylated imldazohnes CHZCHZHFCCPC} substituted in 2-position, by a radical containing from 11-22 carbon atoms selected from the group consisting of alicyclic hydrocarbon radicals, ali- CH1CHT'0*COC1 phatic hydrogen radicals, and aliphatic hydro- A simple example of an oxyalkylated imidazoline carbon radicals substituted by hydroxyl radicals;

radicals, wherein R denotes an alkylene radical 45 having at least 2 and not more than 4 carbon said oxyalkylated imidazolines containing a member of the class consisting of:

radicals, wherein R denotes an alkylene radical having at least 2 and not more than 4 carbon atoms, and n is a Whole number but not over 10, and preferably less than 5.

The intermediate products herein contemplated for reaction with diglycol chloroformate, are characterized by having a five-membered heterocyclic ring with two atoms different from carbon. More specifically, they may be considered as derivatives of imidazole, frequently referred to as glyoxaline, imidazole (glyoxaline) is indicated by the following formula:

Hit it. NH

The imidazolines or glyoxalidines may be considered as dihydroderivatives of imidazole (glyoxaline); and thus the expressions dihydroglyoxalines and glyoxalidines are often employed. The introduction of two hydrogen atoms at the 4-5 position results in the conversion of imidazole into dihydroglyoxalidine, which may be indicated by the following formula:

As to the manufacture of imidazolines, reference is made to the following patents: U. S. Patents Nos. 2,215,861, 2,215,862, 2,215,863 and 2,215,864, dated September 24, 1940, to Waldmann and Chwala.

Imidazolines or glyoxalidines may be regarded as dehydration products of certain amides, and they may be obtained by reacting polyamine and the higher carboxylic acids under certain conditions. The formulation of these glyoxalidine compounds, while forming no part of the present invention, is indicated by the following scheme:

1,2-disubstituted glyoxalidine boxy acids is an expression frequently employed to refer to certain organic acids, particularly monocarboxy acids, having more than 6 carbon atoms, and generally, less than 40 carbon atoms. The commonest examples include the detergentforming acids, i. e., those acids which combine with alkalies to produce soap or soap-like bodies. The detergent-forming acids, in turn, include naturally-occurring fatty acids, resin acids, such as abietic acid, naturally-occurring petroleum acids such as naphthenic acids, and carboxy acids produced by the oxidation of petroleum. As will be subsequently indicated, there are other acids which have somewhat similar characteristics and are derived from somewhat different sources, and are different in structure, but can be included in the broad generic term previously indicated.

Among sources of such acids may be mentioned straight chain and branched chain, saturated and unsaturated, carboxylic, aliphatic. alicyclic, fatty, aromatic, hydroaromatic, and aralkyl acids including caprylic acid, butyric acid, heptylic acid, caproic acid, capric acid, pimelic acid, sebacic acid, erucic acid, saturated and unsaturated higher molecular weight aliphatic acids, such as the higher fatty acids containing at least eight carbon atoms, and including, in addition to those mentioned, melissic acid, stearic acid, oleic acid, ricinoleic acid, diricinoleic acid, triricinoleic acid, polyricinoleic acid, ricinostearolic acid, ricinoleyl lactic acid, acetylricinoleic acid, linoleic acid, linolenic acid, lauric acid, myristic acid, undecylenic acid, palmitic acid, mixtures of any two or more of the above-mentioned acids or other acids, mixed higher fatty acids derived from animal or vegetable sources, for example, lard, cocoanut oil, rapeseed oil, sesame oil, palm kernel oil, palm oil, olive oil, corn oil, cottonseed oil, sardine oil, tallow, soyabean oil, peanut oil, castor oil, seal oils, whale oil, shark oil and other fish oils, teaseed oil, partially or completely hydrogenated animal and vegetable oils, such as these mentioned; hydroxy and alpha-hydroxy higher carboxylic, aliphatic and fatty acids, such as hydroxystearic acid, dihydroxypalmitic acid, dihydroxystearic acid, dihydroxybehenic acid, alphahydroxy capric acid, alphahydroxy stearic acid, alphahydroxy palmitic acid, alphahydroxy lauric acid, alphahydrox myristic acid, alphahydroxy cocoanut oil mixed fatty acids, alphahydroxy margaric acid, alphahydroxy arachidic acid, and the like; fatty and similar acids derived from various waxes, such as beeswax, spermaceti, montan wax, japan wax, coccerin, and carnauba wax. Such acids include carnaubic acid, cerotic acid, montanic acid, psyllastearic acid, etc. As suggested, one may also employ higher molecular weight carboxylic acids derived, by oxidation and other methods, from paraflin wax, petroleum and similar hydrocarbons; resinic and hydroaromatic acids, such as hexahydrobenzoic acid, hydrogenated naphthoic, hydrogenated naphthoic, hydrogenated carboxydiphenyl, naphthenic, and abietic acid; aralkyl and aromatic acids, such as hexahydrobenzoic acid, hydrogenated naphthoic, hydrogenated polycarboxy-diphenyl, hydrogenated naphthenic, and hydrogenated abietic acid; aralkyl and aromatic acids, such as benzoic acid, Twitchell fatty acids, naphthoic acid, hydroxybenzoic acid, and the like.

Other suitable acids include phenylstearic acid, benzoylnonylic acid, campholic acid, fencholic acid, cetyloxybutyric acid, cetyloxyacetic acid, etc.

Another source of suitable acids are those commonly referred to as lac acids, such, for example, as the acids derived from shellac. Such acids include various polyhydroxy acids, for example, aleuritic acid, shelloic acid, and kerrolic acid.

As is well known, one may use substituted acids in which some other non-functional constituent enters the structure of the fatty acid. For instance, one may use aryl-, hydroxy-, alkoxy-, chloro-, keto-, and amino-derivatives. Generally speaking, however, it is always preferable to use the unsubstituted acid, particularly free from substituents which contain either oxygen or nitrogen atoms. Generally speaking, the introduction of hydrocarbon radicals, regardless of source, has little effect, except in altering the hydrophile-hydrophobe balance.

One may also employ the blown or oxidized acids, such as blown ricinoleic acid, blown oleic', etc., or estolides derived from blown oils, such as blown castor oil, blown soyabean oil, etc.

Needless to say, the acids themselves need not be employed, but one may readily employ any functional equivalent, such as the anhydrides, the

acyl chloride, or the like. In some instances, the esters, especially in presence of a trace or a significant amount of water, act as the acid itself, in that the acid is liberated. Unless specific reference is made to a particular isomer,one may employ any isomer or mixture of various isomers, if the acid or acids are so available. We have produced demulsifiers for use in our process by the following procedures:

HYDROXYLATED INTERMEDIATE Example 1 1-aminoethyl-2-heptadecenyl glyoxalidine wasprepared by mixing one gram mole (282 grams) of oleic acid with two gram moles (206 grams) of diethylene triamine, and heating the mixture for a period of about 16 hours under a distilling column. Water was continuously removed until a temperature of about 245 C. was reached. The quantity of water thus removed amounted to about 1.7 moles. Unreacted diethylene triamine was distilled from the reaction mixture under vacuum, and the residue then was purified by distillation at an absolute pressure of 1 mm. of mercury, at which point it boiled within a temperature range of 225 to 250 C. About 220 grams of the 1-aminoethyl-Z-heptadecenyl glyoxalidine was obtained as a pale yellow liquid. The product also may be designated, by reference to the reactants used in its preparation, as oleyl diethylene triamine.

Prior reaction may be indicated in the following manner:

Ethylene oxide was introduced into the above basic compounds on the basis of two gram moles of ethylene oxide for one gram mole of the base. This required 88 grams of ethylene oxide for 349 grams of the base. As is well known, ethylene oxide adds readily to basic compounds having reactive hydrogen atoms. In fact, the addition is so rapid that no catalyst need to be added. This 6 is true in respect to all the basic imidazolines herein described. The time required to introduce 2 moles of' ethylene oxide per mole of the base,

using a temperature of 70 C., and an initial pressure of 60 pounds per square inch, was onehalf hour to 1% hours. At the end of the reaction the pressure dropped to 0 pounds.

The oxyethylated derivative of the previously described compound'may be indicated by the following formula:

NCiHll l C Hz HOCQH;

A further example or variant is exemplified by exactly thesame procedure as before, except using 4 moles ofethylene oxide instead of 2 moles per mole of base. The same comparable compound is obtained, with the exception that an ether, linkage appears, as indicated in the following formula:

' HOC2H4OC2H4 NC2H41I\T I- HOCzH4OC2H4 If 2 mol'es of ethylene oxide were first employed, followed by 2 moles of glycide per mole of base, and assuming uniform distribution, the resultant product would have 4 hydroxyls, as indicated by the following formula:

CZHiOCflH CsHuOCzHA In. subsequent examples concerned with hydroxylated intermediates specifically, in Examples 2 to '7 appearing immediately hereafter, reference of the'sameprocedure as in Example 1 is specifically to the first oxyethylating procedure, as notedin Example 1, to wit, the introduction of 2 moles of ethylene oxide per mole of amine base.

HYDROXYLATED INTERMEDIATE Example 2 The base used in the preceding example was replaced by l-(aminoethyl ethylamino)-2-heptadecenyl glyoxalidine. This glyoxalidine was prepared by reacting 1 gram mole of oleic acid with three gram moles (438 grams) of triethylene' tetramine in a vessel equipped with a distilling column. The mixture was heated for a period of about 6 hours, and water was continuously removed until a temperature of about 300 C. was reached. Approximately 1.9 moles of water were thus removed. The reaction mixture was then distilled under vacuum to remove excess triethylene tetramine.

It is to be noted that this compound contained the following linkage:

HOCzH4 cals. When subsequent reaction takes place between 2 moles of the glyoxalidine and one mole ethylene oxide (mole ratio 1:3).

7 of diglycol chloroformate, it appears impossible to determine whether the reaction has involved the residual amino hydrogen atom or the alcoholic atoms, or if a mixture is formed. As far as the final product is concerned, it is absolutely immaterial. When 3 or more moles of alkylene oxide, such as ethylene oxide are employed, all 3 amino hydrogen atoms are converted into an alkanol radical, and thus amides cannot be formed. The resultant of the above reaction involving the acid and the tetramine was a yield of approximately 390 grams of the imidazoline. This represented one gram mole. We divided this amount into two halves, each half representing, roughly, 190 grams. We treated one-half gram mole with one mole of ethylene oxide (mole ratio 1:2) and we treated the other half With 66 grams of The ethylene oxide was added under substantially the same time, temperature, and pressure conditions, as noted under Example 1, preceding. As stated before, ethylene oxide adds with extreme rapidity.

HYDROXYLATED INTERMEDIATE Example 3 An imidazoline was obtained from oleic acid and tetraethylenepentamine by using equimolar amounts. No attempt was made to use an excess of the amine and to distil out the excess subsequently. This procedure does not give quite as satisfactory a yield as following the procedure described under Examples 1 and 2, preceding, for the manufacture of the imidazoline. However, it is perfectly satisfactory for use as an interme diate in the process described.

Approximately 435 grams of the imidazoline was obtained employing 190 grams of the polyamine and 282 grams of oleic acid. This was divided into thirds and 145 grams were employed in each of three separate oxyethylation In the first oxyethylation the molal ratio employed Was 1:2. Thirty grams of ethylene oxide was added to 145 grams of the imidazoline. In the second procedure, the molal ratio employed was 3:1. Forty-four grams of ethylene oxide was added to 145 grams of the imidazoline. In the third procedure a mola-l ratio of 4:1 was employed. In this instance, 60 grams of ethylene oxide was employed for 145 grams of the imidazoline. In each instance, the ethylene oxide was added under the same time, temperature, and pressure conditions noted under Example 1, preceding. As previously noted, ethylene oxide adds to this reactant with extreme rapidity.

In this instance, the following radical appears in the glyoxalidine:

Thus, in this case as much as 3 moles of ethylene oxide or other suitable alkylene oxide could be employed and still leave an amino group susceptible to reaction. See what is said previously in regard to the prepared variants. This compound, as described, and the previous one involving the use of glycide, illustrates the fact that one mole of a suitably selected glyoxalidine can react with a mole of diglycol chloroformate. It is advantageous, however, to use the reactants in the ratio of 2 moles of the glyoxalidine and one mole of the chloroformate.

The use of tetroethylyenepentamine also illustrates another fact, as is well known, to wit: that one mole of such a compound, the pentamine,

8 for example, can be reacted with 2 moles of oleic acid or other selected reactant, to introduce 2 glyoxalidines rings, one being at each terminal. The formula for such a compound is obvious and does not require further elaboration.

HYDROXYLATED INTERMEDIATE Example 4 Lauric acid is substituted as a reactant for oleic acid in the three preceding examples.

HYDROXYLATED INTERMEDIATE Example 5 Ricinoleic acid is substitued for oleic acid in Examples 1 to 3, preceding.

HYDROXYLATED INTERMEDIATE Ezrample 6 Naphthenic acid derived from Gulf Coast crude, and having a molecular weight of approximately 220, is substituted for oleic acid in Examples 1 to 3, preceding.

HYDROXYLATED INTERMEDIATE Example 7 An equivalent molal amount of propylene oxide is substituted for ethylene oxide in Examples 1 to 6, preceding.

The preferred type of demulsifier is obtained by the action of 1 to 5 moles of the oxyalkylating agent, for instance, ethylene oxide or propylene oxide, on one mole of the imidazoline.

Where the hereto appended claims specify the presence of a member of the class consisting of radicals, i. e., the group introduced by oxyalkylation at the amino hydrogen position, it is understood that R includes groups derived from ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide. As stated, 11. represents the numeral 1 to 10, and preferably, not over 4.

Actually, a somewhat different variation can be employed in the manufacture of the oxyalkylated imidazolines. For example, ethylenediamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine can be treated with a mole of ethyleneoxide or propyleneoxide or butyleneoxide, or glycide or methylglycide, so as to yield the corresponding derivative having a hydroxyalkyl attached to one terminal nitrogen and the structure at the other end remaining unchanged. Such compound can be reacted in the usual manner with an acid, such as oleic acid, stearic acid, or the like, to produce the oxyalkylated imidazoline.

Another procedure which avoids this particular step is to simply purchase the hydroxyalkylated material in the open market. Thus, one may obtain the hydroxyethyl, hydroxypropyl, hydroxybutyl, or other equivalent ethylenediamine. 2-aminoethylethanolamine (hydroxyethyl ethylenediamine) is sold as a commercial product and can be reacted with a variety of the higher fatty acids previously noted.

If desired, one does not even have to go to this much trouble and can purchase l-hydroxyethyl- 2-heptadecenyl glyoxalidine. As previously Me as stated, this particular compound has the follow-, ing structure:

The corresponding heptadecyl compound has the following structure:

The corresponding ricinoleyl derivative has the following structure:

Thus, the simplest procedure for manufacturing the herein specified compounds is simply to purchase l hydroxyethyl-2-heptadecenyl glyoxalidine and react it in the proportion of 2 moles of such glyoxalidine with one mole of diglycol chloroformate. The following examples illustrate the manufacture of the compounds or products herein described and intended for use in various industrial arts, particularly for emulsification of petroleum emulsions.

CATIONIC POLYCHLORIDES Example 1 2 gram moles (700 grams) of l-hydroxyethyl- 2-heptadecenyl glyoxalidine were mixed with 1 gram mole (231 grams) of diglycol chloroformate and heated under a reflux condenser for 1 hour at 160 to 180 C. On cooling, a wax-like solid resulted. It was very soluble in water and gave a solution which foamed vigorously on shaking. In this connection it is to be noted that both reactants, to wit, the amine and the chloroformate, are water-insoluble prior to reaction.

CATIONIC POLYCHLORIDES Example 2 The same identical procedure was followed as in Example 1, preceding, except that the hep-. tadecyl compound was substituted for the heptadecenyl compound. The time of reaction was a little bit longer, to wit, 1 hours, and the temperature employed slightly higher, 170 to 185 C. The material obtained was more solid than in the previous example, but was soluble, particularly in warm water. As in said Example 1,,- the molar ratio represented two moles of the amino compound for each mole of the diglycol chloroformate.

CATIONIC POLYCHLORIDES Example 3 The same procedure was followed as in Example 1, preceding, except that the ricinoleyl derivative was employed instead of the heptadecenyl derivative. The product showed approximately the same consistency as in Example 1, except with a tendency to be somewhat softer. No effort was made to determine whether or not the chloroformate had reacted to any extent at the ricinoleyl hydroxyl. As in Example 1, the molar ratio represented two moles of the amino compound for each mole of the diglycol chloroformate. 76

10 CATIONIC POLYCHLORIDES Example 4 Exactly the same procedure, without variation, was followed as in Example 1, preceding, except that the oxyalkylated imidazoline obtained by reaction between 2 moles of ethylene oxide and 1 mole of 1-aminoethyl-2-heptadecenyl glyoxalidine was substituted for l-hydroxy-ethyl-Z-heptadecenyl glyoxalidine. The dihydroxylated compound herein employed as a reactant was described previously herein. The appearance of the final product was about the same as in Example 1. As in Example 1, the molar ratio represented 10 two moles of the amino compound for each mole of the diglycol chloroformate.

CATIONIC POLYCHLORIDES Example 5 Exactly the same procedure, without variation, was followed as in Example 1, preceding, except that the oxyalkylated imidazoline, obtained by reaction between 2 moles of ethylene oxide and one mole of l-(aminoethyl ethylamine) -2-heptadecenyl glyoxalidine, was substituted for l-hydroxyethyl-2-heptadecenyl glyoxalidine. The dihydroxylated compound herein employed as a reactant has been described previously. The appearance of the final product was about the same as in Example 1. As in Example 1, the molar ratio represented two moles of the amino compound for each mole of the diglycol chloroformate.

' CATIONIC POLYCHLORIDES Example 6 CATIONIC POLYCHLORIDES Example 7 The same procedure was followed as in Example 4, preceding, except that the amine employed was derived by reaction between 4 moles of ethylene oxide (insteadof 2 moles of ethylene oxide) and one mole of l-amino-ethyl-2-heptadecenyl glyoxalidine. The composition of this amine was as follows:

N H0 021140 02H, R 0 CHz NC2H4II (3H2 H 0 02114 O C2114 The appearance of this product and its solubility is the same as in Example 4, preceding, except that it showed somewhat greater solubility and was somewhat less solid than the product obtained in Example 1.

As previously pointed out, ethylene oxide in the previous examples can be replaced by any of the other alkylene oxides previously described having not over 4 carbon atoms, for instance, ethylene oxide, and can be replaced by an appropriate amount of another suitable alkylene oxide, such as propylene oxide, butylene oxide, glycide or methylglycide. Where the amine reactant contains a plurality of reactive hydrogen atoms, one mole of diglycol chloroformate can be reacted with one mole of the amine reactant. It is advantageous, however, to use 2 moles of the amine reactant for one mole of the diglycol chloromeans exhaustive. The most important phase of the present invention, as far as industrial application goes, is concerned with the use of the materials previously described as demulsifiers for water-in-oil emulsions, and more specifically, emulsions of water or brine in crude petroleum.

Having thus described our invention, what we claim as new and desire to secure by Letters Patent is:

formate. In the various derivatives obtained in 1 A cation-active polychloride which is the the manner described there may be combination reaction product of diglycol chloroformate and an between a divalent diglycol chloroformate radical oxyalkylated imidazoline substituted in the 2-poand 2 oxygen atoms, or between 2 nitrogen atoms, sit ion by a radical containing 11 to 22 carbon or between an oxygen and a nitrogen atom, or atoms selected from the group consisting of aliin the event that the amine derivative is derived 15 cyclic hyd a bon radicals. aliphatic hydrocarfr m ricinomc acid, hydroxystearic a id, dihybon radicals, and aliphatic hydrocarbon radicals droxystearic acid, or the like, it is possible, and in substituted by hy l ra a s; sa d y l y fact probable, that such alcoholic hydroxyl-hyated imidazfflines Contaming a member of the drogen atoms are similarly reactive and further class consisting of variations are thus obtained. Previous reference has been made to the fact that tetraethylenea d pentamine may be reacted with 2 moles of a higher fatty acid, such as stearic acid, oleic acid,

or the like, and the resultants subjected to oxyalkylation. Similarly, one might employ one mole of a high m lal acid, Su s 01816 Or Stearic radicals linked to the imidazoline structure acid, and one mole of a low molal acid, such as throu h th nitrogen atom in the 1-position, acetic acid, ydroxyacetic acid, lactic ac d. o t e wherein R denotes an alkylene radical having at like. In light of what has been said, it is obvious least 2 and not more than 4 carbon atoms and n that the formula can only be drawn so as to is anumeral from lto 10.

indicate the structure of the simpler derivatives 2, The product of claim 1, wherein the amine herein described. A reaction product derived reactant contains one imidazoline ring structure from pentaethylenehexamine and one or two only.

moles of a higher fatty acid, such as oleic acid. 3. The product of claim 1, wherein the amine can be united with 2 moles of diglycol chlororeactant contains one imidazoline ring structure formate to yield a polychloride having 4 chloride only, and the radical substituted in the 2-position ions. Reactions m y also e place in which is an aliphatic radical derived from a higher fatty only one acyl chloride radical of the diglycol id,

chloroformate reactants with the amine react- 4; The product of claim 1, wherein the amine a t- The e c mp Ones can only be dereactant contains one imidazoline ring structure scribed in terms of manufacture, i. e., as the prodonly, and the radical substituted in the 2-position uct or resultant of the reaction between diglycol is an aliphatic radical derived from an unsatuehloroformate and the specified amine reagents. rated higher fatty acid.

Materials of the kind herein specified are useful 5. The product of claim 1, wherein the amine as wetting, detergent, and leveling agents in the reactant contains one imidazoline ring structure laundry, textile, and dyeing industries; as wetting. only, the radical substituted in the 2-position is agents and detergents in the acid washing of an aliphatic radical derived from an unsaturated fruit, in the acid washing of building stone and higher fatty acid, and R is an ethylene radical. brick; as a wetting agent and spreader in the 6. The product of claim 1, wherein the amine application of asphalt in road building and the reactant contains one imidazoline ring structure like; as a constituent of soldering flux preparaonly, the radical substituted in the 2-position is tions; as a flotation reagent in the flotation sepaan aliphatic radical derived from an unsaturated ration of various minerals; for flocculation and higher fatty acid, and R is an ethylene radical, coagulation of various aqueous suspensions conwith the proviso that the ratio of amine reactant taining negatively charged particles, such as sewto diglycol chloroformate is 2:1. age, coal washing waste water, and various trade 7. A compound of the composition indicated by wastes, and the like; as germicides, insecticides, the following formula:

N--orh CH2-N Curin 5H! (BHZ CnHz:

emulsifiers for cosmetics, spray oils, water-repellent textile finish, etc. These uses are by no Ci'IHn HOHaCHzOIO C 0C2Hlo 0211400010 OHKCHZE 8. A compound of the composition indicated by the following formula:

13 14 9. A compound of the composition indicated by through the nitrogen atom in the 1-position, the following formula: wherein R denotes an alkylene radical having at NCH2 CH2-N H I J H [Oll- OHCUHEQC CH2 H2 COHHHOH [CIT 10. A method for the manufacture of cationm least 2 and not more than 4 carbon atoms, and 11 active polychlorides, characterized by reacting is a numeral from 1 to 10. diglycol chloroformate with an oxyalkylated imidazoline substituted in the 2-position by a MELVIN DE GROOTE. radical containing 11 to 22 carbon atoms selected BERNHARD KEISER. from the group consisting of alicyclic hydrocarl5 bon radicals, aliphatic hydrocarbon radicals, and

aliphatic hydrocarbon radicals substituted by REFERENCES CITED hydroxyl radicals; said oxyalkylated imidazolines The following references are of record in the containing a member of the class consisting of file Of this Pa ent:

and UNITED STATES PATENTS (B4)) H Number Name Date 2,262,743 De Groote et a1. Nov. 11, 1941 -RN\ 2,369,818 De Groote et a1. Feb. 20, 1945 (R O)nH 25 2,400,394 De Groote et a1. May 14, 1946 2,468,180 V De Groote et al. Apr. 26, 1949 radicals linked to the imidazoline structure 

1. A CATION-ACTIVE POLYCHLORIDE WHICH IS THE REACTION PRODUCT OF DIGLYCOL CHLOROFORMATE AND AN OXYALKYLATED IMIDAZOLINE SUBSTITUTED IN THE 2-POSITION BY A RADICAL CONTAINING 11 TO 22 CARBON ATOMS SELECTED FROM THE GROUP CONSISTING OF ALICYCLIC HYDROCARBON RADICALS, ALIPHATIC HYDROCARBON RADICALS, AND ALIPHATIC HYDROCARBON RADICALS SUBSTITUTED BY HYDROXYL RADICALS; SAID OXYALKYLATED IMIDAZOLINES CONTAINING A MEMBER OF THE CLASS CONSISTING OF 